4&#39;-methyl-6-halogen thioindigos and their 6&#39;-halogen derivatives



Patented Jan. 19, 1932 UNITED STATES PATENT oF IcE RICHARD IIIIIEJIRZ, OF FRANKFORT-Ofi-THE-MAIN, AND WALTER .BR'UNNIIR; OF FRANK- FORT-ON-THE-MAIN-FECHENHEIM, GERMANY, AssIGNoRs To GENERAL ANILINE WORKS, INC., OFNEW YORK, IN. Y.,- A CORPORATION-OF DELAWARE 4MET'HYL-6-HALOGEN THIOINDIGQS AND THEIR 6-H.ALOGEN DERIVATIVES I No Drawing. Application filed. August 24, 1929, Serial no. 388,256, and. in Germany septe mbero 923.

Our present invention relates to new vat dyestuffs of the thioindigo series which are obtainable by condensing together two compounds corresponding to the general formulae:

'OHa.

-' to the general formula wherein Y means hydrogen or halogen.

They dye cotton from a hydrosulfite vat 184.4 parts of 6-chloro-3-hydroxy-thionaphthene are dissolved in about 4,000 parts of glacial acetic acid. To this solution 864 parts of 4-methyl-6-chloro-2.3-dihydro-3- ketO-thionaphthene-Q- (para-dimethylaminoanil), obtainable for instance by acting with para nitroso-dimethylaniline on an alkaline green solution, 1 dyeing cotton 'from a vat bright bluish pinkshades.

.ample 1..

solution ed for some time until the formation of the dyestufi is finished. The precipitated dyestufl is filtered 01f. It corresponds to the formula OH V It represents when dry 7 a dark red powder soluble inconcentrated sulfuric acid to a yellow Example 2 '1 3-hydroxy-4-methy1-6-chl o r 0 th i on ap h thene is condensed with 6-choro-2.3-dihy- 'dro 3 keto-thionaphthene 2-anil 1 in the manner described in Example 1. The dyestufi :of 3-hydroxy'-4-methyl 6echloro- H thionaphthene, are'addedp The mass is heata thus obtained is identical to thatof Example 1.

' Emample3- s i, I 6-bromo-3rhydroxy-thionaphthene is condense'd with '4-methyl-6-bromo-2.3-dihydro- 8 keto thionaphthene-Q- (para-dimethylamino-anil in the manner described in Example 1. The dyestufl? thus obtained corresponds to the formula I j u n C C It shows similar Example 4 properties as that of Ex I 6-chloro-thionaphthene is replaced by 3-hy- 1 droxy-4-methyl-thionaphthene and the process 1s otherwise carried out in like manner,

I the formula a new dyestufi is obtained which corresponds to the formula O- O=O anddyes cotton bright bluish pink shades.

We claim: 1. As new compounds thevat dyestu fls of the general formula V i i V X i Y s/ s wherein X stands for a'clilori'ne or bromine atom and-Y represents hydrogen or a chlorine or bromine atom, Which compounds are when dry dark red powders; soluble in concentrated sulfuric acid to greenish solutions, dyeing cotton from yellow vats bluishpink to .red shades r 2. As a new compound the vat dyestufl of the formula W I which compound is when dry a dark red powder, soluble in concentrated sulfuric acid to a green solution, dyeingcotton from a yellow Vat bluish pink'shades.

3. As a new compound the vat dyestuff of the formula:

7 CH5 Q 4 l /gl which compound is soluble in concentrated sulfuric acid to agreenish solution and dyes cotton from a yellow vat bluish pink shades. 4

- 4. As anew-compound'thevat dyestuff of Oils Which compound is soluble in concentrated sulfuric acid to a greenish solution and dyes cotton from a yellow vat bright bluish pink shades. I

In testimony whereof, We afiix our signatures.

RICHARD HER Z. -WALTER BRUNNER. 

